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FCC MANUAL 5.

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FCC UNIT MONITORING

SUMMARY

Monitoring and optimization of the performance of the FCC can add significantly to
the overall refinery margins. It requires careful data collection and validation
procedures to ensure a proper evaluation can be made and the right conclusions
drawn. The relevant data include the unit conditions, feedstock properties, product
yields and qualities, as well as the E-cat analyses.

We will review some of the elements of unit monitoring essential for assessing
catalyst effects and optimizing the unit performance. We also highlight Albemarle’s
unit monitoring service which is available to assist our clients.

CONTENTS
1. Process variables
2. Feedstock characterization
3. Heat balance calculation
4. Cut-point corrections
5. Performance evaluation
6. Monitoring services

1. PROCESS VARIABLES

Unit monitoring includes data collection, validation, and interpretation. The number
(and quality) of available measurements will determine the extent of the evaluation
possible. Required data can be grouped as:

1. Mass balance data (product flows, densities)


2. Heat balance data (temperatures, flue gas composition, air rate)
3. Feedstock characteristics (density, refractive index, sulfur, metals, etc.)
4. Essential product properties (distillations, octanes, sulfur, viscosity, CP/PP)
5. Equilibrium catalyst analyses (activity, chemical and physical properties)

For a complete overview of the data normally needed for monitoring, refer to the
Albemarle FCC Questionnaire (see APPENDIX).

In most cases heat and material balance data are available on a continuous basis from
the process computer. Feed and product analyses are usually available on at least a
weekly basis from the laboratory. The E-cat analyses are usually conducted weekly.
To minimize analysis expenses, the essential product properties should be properly
defined by the refinery engineer. It is also critical that analyses are conducted on

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samples taken at the same time, during operations held constant before and during
sampling.

This information allows proper monitoring of the FCC. The frequency of feed and
product samples depends on the size of the operation, the (non-)steadiness of feed
quality and operating variables, and specific needs such as quantifying catalyst
changes. The reliability of data can be improved by careful validation, which is an
essential element of unit monitoring.

Often, by plotting trends or looking through the data, outliers (data points outside the
normal range) can be detected. However, an outlier is not necessarily erroneous. For
example, feed densities in the FCC typically range from 0.900 to 0.920 – but a density
of 0.925 is reported recently. It looks suspicious, but plotting against refractive index
shows the value to fall on the expected line (figure 1) (1).

Figure 1: Validation of FCC feed properties

Feedstock properties are regarded as independent variables in the FCC operation.


Other independent variables are flow rates, some temperatures and pressures, which
are mostly controlled by instrumentation and can be adjusted as desired by the
operator to optimize performance. Dependent variables react to changes in the
independent variables, for instance to maintain the unit in heat balance (2).
Independent variables that affect the heat balance can be classified based on their
influence on coke production (coke/feed) or delta coke (coke/catalyst), shown in table
1.

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Table 1: Independent FCC variables that influence the heat balance

Effect on coke yield Effect on delta coke Effect on both


feed rate feed properties recycle feed rate
feed preheat reactor pressure riser outlet temp
catalyst cooling catalyst activity dispersion steam
air temp/humidity catalyst selectivity stripping steam

Coke yield and delta coke are examples of dependent variables that can only be
changed indirectly, by manipulating independent variables. Tedious calculations are
needed to estimate such heat balance changes and predict the effects of independent
variables properly. This is true also of variables such as gasoline octane and unit
conversion. Unit monitoring can provide a basis for calculations, from previous
operating data, using simple statistics. For instance, effects of frequent changes in
feedstock quality on product yields and properties can be predicted from existing
experience. When evaluating a switch to a new catalyst, the same calculations can
normalize unit data to constant conditions and feed quality. However it is preferred to
apply a process simulator for proper separation of effects of feed quality, unit
operating conditions, and catalyst type.

2. FEEDSTOCK CHARACTERIZATION

Crude oil is not a uniform material. Its composition can vary not only with location
and age of the oil field, but also with the depth of the individual well. On a molecular
basis, petroleum is a complex mixture of hydrocarbons plus organic compounds of
sulfur, oxygen, and nitrogen, as well as compounds containing metallic constituents,
particularly vanadium, nickel, iron and copper.

Various methods exist to estimate hydrocarbon composition or carbon atom


distributions in FCC feeds, as published by ASTM, API and some oil companies (3).
However, unit performance is often explained adequately using just the basic analyses
such as density, refractive index, or aniline point directly, without conversion into
compositional breakdowns. The carbon atom distribution can be used to estimate the
maximum crackability of the feedstock. Actual unit limits may not permit this level
of conversion. Typical limitations are air blower or gas compressor capacities and the
regenerator temperature that is controlled by delta coke.

One correlation of conversion with feed density is shown in figure 2. Similar


correlations can be made using refractive index or aniline point of the feed. When
large variations in feed boiling range occur, the UOP or Watson K factor (see
ATTACHMENT), calculated from average boiling point and density, can be helpful.
The hydrogen content is especially useful for hydrotreated feeds. Different methods
exist for estimating hydrogen, depending on the feed analyses available (attachment).
This can permit another validation of unit data, by evaluating the hydrogen balance.

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Figure 2: Interaction of feed quality and unit limitations

The standard analyses performed on FCC feedstocks may not be sufficient when the
feed composition changes significantly over the boiling range of the feed. It is known
for example that the aromatics distribution also affects product yields and properties.
Figure 3 shows the impact of mono-aromatics in feedstock on gasoline MON.

Figure 3: Effect of feed mono-aromatics content on gasoline MON

The mono-aromatics in feed do not necessarily correlate with standard analyses.


Moreover, FCC feedstock may contain other streams that disturb the “normal”
distributions of hydrocarbons, such as cracked stocks or hydrotreated material. In
such cases, we need better analysis tools or even performance testing to identify
feedstock effects. The catalyst and feedstock effects on the FCC unit performance are
often interrelated, especially when the unit is continuously operated against its
hardware limitations. This complicates catalyst selection, and subsequent evaluation.
With other operating conditions constant, catalyst ranking can change with feedstock

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quality shifts. An illustration is in table 2, with test data on fresh catalysts
impregnated with 1000 ppm nickel.

Table 2: Effect of feedstock quality on catalyst ranking


(MAT data at constant cat/oil ratio)

Feedstock Kuwait VGO Statfjord resid


Catalyst A B A B
Conversion 68.0 71.1 67.2 60.2

3. HEAT BALANCE CALCULATION

In a commercial unit, the coke production will always be such that the energy released
by its combustion keeps the unit in heat balance. This energy is used in the
regenerator to:

• heat spent catalyst from stripper outlet to regenerator bed temperature


• heat air from blower discharge to flue gas temperature
• compensate for heat losses from the regenerator

The heat transferred by the circulating catalyst provides energy for:

• vaporization of feed/recycle, and heating vapors to riser top temperature


• heating any riser fluidization/dispersion steam or gas
• heating stripping steam to stripper temperature
• compensating for heat losses from the reactor/circulation lines
• cracking the oil (heat of reaction)

The regenerator mass balance provides the air/coke and hydrogen/coke ratios,
whereas the heat balance is used to calculate the cat/oil ratio (from regenerator side
balance) and the heat of cracking (reactor side). The typical calculations are
straightforward, but the level of detail included can vary considerably. For instance,
the heat losses, heat of desorption of coke and catalyst specific heat are not precisely
known, and are normally assumed constant. More typical problems affecting the
balances are inaccuracies in flue gas analyses and air rates. In practice these
uncertainties may lead to erratic values for cat/oil ratio, and even for coke yield.
Sometimes the hydrogen in coke (typical 6-8 wt%) and heat of reaction (discussed
below) can be used to check the heat balance.

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We have developed simple correlations to check the heat balance of the reactor and
regenerator (figure 4). When unit data do not permit a complete heat balance
calculation, it is possible to estimate delta coke and coke make using these formula

(figure 5) (4,5).

Figure 4: Simplified heat balance correlations (4)

Figure 5: Validation of heat balance data

In the two figures above, RGT is regenerator dense bed temperature, RXT is riser
outlet, CFT the combined feed temperature and CFR the combined feed ratio. The
ratio of combustion and preheat factors varies around 5. The heat of reaction
increases with the number of moles produced, e.g. the conversion level. Catalyst
effects are small and probably within the accuracy of the data. Ultrastable zeolites
(USY) used in octane catalysts show a slightly higher heat of cracking (figure 6),
because there is less exothermic hydrogen transfer and hence more olefinic products.

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Figure 6: Effect of conversion on the heat of reaction

4. CUTPOINT CORRECTIONS

The amount of data needed to monitor product yields and qualities can be
considerable, but normalization or standardization of product cutpoints can assist this
effort. It is quite helpful to calculate conversion (wt or vol%) at a constant cutpoint,
typically 221ºC (430ºF) on true boiling point (TBP) basis. There is however no
universal procedure to perform this and related standardization of cuts; different
methods may give varying results.

The incomplete separation of products from the main fractionator makes it difficult to
simplify the cutpoint correction. Many units run far over design capacity, so that
distillation data show large overlaps between adjacent cuts. This can be circumvented
by taking samples of the total product from the reactor overhead, prior to entry in the
main column. But the sampling procedure is too complicated to use routinely for unit
monitoring, and is more usually employed for specific unit or catalyst testing(6).

In principle, complete distillation curves of the various liquid products are required to
make reliable cutpoint corrections. In practice, most refineries use ASTM or GC
simdist analyses. Conversions to TBP are possible but not very accurate, producing
irregularities in the shape of the total product distillation curve.

The preferred method to calculate corrected yields and product properties from plant
data is to resynthesis the total product assay by computer simulation. Straight-cut
yields at any given cutpoint can then be calculated, along with corrected product
properties. A simplified manual method is shown in figure 7 for correcting cutpoints,
plotting accumulated yields against the natural logarithm of the 50% ASTM points.
The liquid volumes are accumulated yields from one 50% yield to the next:

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• LCN point is at 50 vol% of LCN on feed
• MCN point is at 50% of MCN on feed + all LCN vol% on feed
• etc.

Figure 7: Example of cutpoint correction method

5. PERFORMANCE OPTIMIZATION

In our technical service group, a process simulator is used to evaluate the potential
changes in product yields and properties during a catalyst switch. In practice the
individual FCC may still react differently on a specific catalyst than expected, and this
can have a severe impact on the economics (positive or negative). FCC unit
monitoring has become a tool to establish, interpret and predict the changes in product
yields and properties for individual cases.

An example of several years of unit monitoring is discussed below. Weekly test run
data are averaged over periods with the same catalyst in use. In this way an
interesting data base is obtained with the possibility to investigate catalyst effects. In
total, eight different catalysts are compared in the data base. The feedstock
composition did not change dramatically, but there is large variation in feed
paraffinicity (figure 8).

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Figure 8: Correlation of feedstock properties

In the drive for maximum gasoline octane and LPG olefins, catalysts with lower
RE2O3 are used in this refinery. Figure 9 shows the effect of equilibrium RE2O3 on
gasoline RON. The corrected octane is calculated from average RON after adjusting
it for constant gasoline cutpoint, riser outlet temperature, and feed density. In this
way, catalyst effects become more visible.

Figure 9: Effect of equilibrium RE2O3 on gasoline octane

Different unit limitations have played a role in the catalyst selection for this refinery,
e.g.: feed preheat capacity (to compensate added heat of cracking); gas compressor
capacity (to cope with increased hydrogen and light gases); and, maximum
regenerator temperature (with less efficient stripping of high surface area catalysts).

The reduction in RE2O3 also resulted in a lower catalyst activity, and lower E-cat
surface area. The catalyst activity is corrected for a constant addition rate. In

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practice, catalyst consumption is increased to maintain the equilibrium activity when
using low rare earth catalysts, to avoid loss of conversion. Some catalysts showed
too much deactivation, either from higher regenerator temperatures or insufficient
activity retention (figure 10).

Figure 10: Effect of equilibrium RE2O3 on catalyst activity

The effect of catalyst activity is displayed in figure 11. The conversion (at 221 ºC
cutpoint) is corrected for feed density and rate, and reactor temperature. Maximum
conversion is at about 66 wt% MST activity. At higher activity, conversion drops due
to increased delta coke on catalyst, resulting in higher regenerator temperatures and
hence lower cat/oil ratios. The regenerator temperature was however more sensitive
to E-cat surface area, due to inadequate stripper efficiency (figure 12).

Consequences of high regenerator temperatures are increased deactivation as well as


substantial increase in thermal cracking, shown in figure 13. For catalytic cracking,
C4/LPG is close to 70 wt%, while this ratio can drop well below 60% when thermal
cracking is extensive. Economic evaluations indicate that the optimum rare earth
level in this unit is about 1 wt% on catalyst (figure 14). This depends on the values of
the different products, and gasoline octane in particular.

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Figure 11: Effect of catalyst activity on conversion

Figure 12: Effect of E-cat surface area on regenerator temperature

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Figure 13: Monitoring thermal cracking in FCC

Figure 14: Optimizing FCC margins with catalyst rare earth content

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6. MONITORING SERVICES

The joint evaluation of FCC unit data by the refinery’s and Albemarle’s technical
service staff has become a major tool in evaluating unit and catalyst performance. In
general, the monitoring activities include the following steps:

• data collection
• validation (essential)
• analysis
• catalyst evaluation
• recommendations

The objective of this work is to improve the economics of FCC operation. Special
forecasts can be made to optimize profitability against the unit limits, by e.g. variation
of feed rate or other operating parameters. Consistent and competent monitoring of
the unit performance offers the opportunity to ensure that the catalyst in use is at the
optimal activity level (and in fact if catalyst formulation needs revision), to improve
operations further, or to accommodate process and feedstock changes. It also
provides a data base for long term review of process and hardware operations, which
can flag developing problems for correction.

A full report with recommendations is sent to the refinery on an as-agreed basis,


typically quarterly, and discussed during the routine visits of Albemarle’s technical
service staff. Presentations are made to refinery management as well.

Refineries world-wide have appreciated this service and recognized the importance of
Albemarle’s unit monitoring service for the continuous improvement of their FCC
operations. A complete demonstration of the monitoring system can be made on
request at the refinery.

REFERENCES

1. R. C. Pinto, B. van Keulen, “Statistical evaluation of commercial FCC data”,


2nd South American Catalysts Seminar, 1987.
2. J. R. Murphy and Y. L. Cheng, “Interaction of FCC variables can be
predicted”, Oil & Gas J., Sep. 3, 1984.
3. H. Dhulesia, “New correlations predict FCC feed characterization”, Oil & Gas
J., Jan. 13, 1986, 51-54.
4. B. van Keulen, “Model shows reducing delta coke benefits FCC operation”,
Oil & Gas J., Sep. 26, 1983.
5. B. van Keulen, A. Gevers, and A. Blum, “FCC unit monitoring and technical
service”, Akzo Catalysts Syposium, 1986.
6. P. R. Satbhai, J. M. H. Dirkx, R. J. Higgins, and P. D. L. Mercera, “Best
Practices in Shell FCC Units,” Akzo Nobel Catalysts Seminar, Mumbai India,
Oct. 1998.

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APPENDIX: ALBEMARLE FCC QUESTIONNAIRE

Refinery Date

General Information Fresh Feed Properties


FCC Design / Licenser Feed rate t/h
Type RX Bed/Riser/SCT SG or °API
MTBE m3/h Sulfur wt%
Alkylation m3/h Concarbon wt%
Polymerization m3/h Total / Basic N ppm /
Ni / V ppm /
Operating Conditions Aniline Point °C
Combined feed T °C Refractive Index / @ °C /
Reactor T °C Distillation Type TBP / ASTM
Reactor P barg IBP °C
RG1 / RG2 bed T °C / 5% °C
RG1 / RG2 P barg / 10% °C
Flue gas T °C / 30% °C
Dilute Phase T °C / 50% °C
Air rate kNm3/h / 70% °C
Ambient °C / humidity / 90% °C
O2 Addition kNm3/h / 95% °C
Regen Air Inlet T °C / FBP °C
Fluegas CO2 vol% / Viscosity cSt / @ °C /
CO vol% /
O2 vol% / Recycle Streams
SOx ppm / HCO Recycle t/h
NOx ppm / Slurry Recycle t/h
Stripper Steam Flow t/h
Dispersion Steam t/h Equililbrium Catalyst
Dispersion Water t/h MAT wt%
Lift Gas t/h Sb / Bi ppm /
Cat. Cooler Mkcal/h Ni / Cu ppm /
Cat. Circulation t/min Na / V ppm /
Cat.-to-Oil Ratio t/t Carbon wt%
Contact time, sec RE2O3 wt%
Al2O3 wt%
Fresh Catalyst Surface Area m2/g
Current Type SA zeolite / meso m2/g /
RE2O3 wt% ABD g/ml
Al2O3 wt% PSD: -105 / -80 wt% /
SA m2/g -60 / -40 wt% /
Inventory tons APS micron
Addition Rate t/d
Catalyst Losses t/d
Losses RX / RG t/d /
Combustion Promoter
Other additives

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Fresh Feed Compostion, vol% / wt% Unit Constraints Min / Max
Hydrotreated feed Reactor T °C /
Vacuum gas oil Regenerator T °C /
Coker gas oil Feed Preheat T °C /
Atmospheric resid Dry Air Rate kNm3/h /
Vacuum resid Catalyst circulation t/h /
Slops Compressor kNm3 /
Others Absorber gas kNm3/h /
Debutanizer t/h /
Slurry t/h /
Other /

Yields wt% Economic Values


H2 FCC Feed / resid $/bbl /
H2S Fuel Gas/Coke $t /
C1 LPG sat / olefins $t /
C2 LCN /HCN $/bbl /
C2= LCO / HCO $/bbl /
C3 Slurry $/bbl
C3= RON / MON $/OB /
iC4
nC4 Major Objectives for optimization
i=Butene 1.
Butene-1 2.
Butadiene
t-Butene-2 Fractionated product analyses
c-Butene-2 LCN
C5 - LCN* SG or °API
HCN* Distillation Type TBP / ASTM
LCO* IBP °C
HCO* 5% °C
Slurry* 10% °C
Coke 30% °C
Balance 50% °C
70% °C
90% °C
95% °C
FBP °C
RVP psia
Sulfur wt%
RON / MON Clear /
RON loss in posttreater
MON loss in posttreater
Olefins content, %

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Fractionated product analyses (continued)
MCN / HCN / LCO
SG or °API / SG or °API /
Distillation Type TBP / ASTM Distillation Type TBP / ASTM
IBP °C / IBP °C
5%°C / 5% °C
10% °C / 10% °C
30% °C / 30% °C
50% °C / 50% °C
70% °C / 70% °C
90% °C / 90% °C
95% °C / 95% °C
FBP °C / FBP °C
RVP psia / Cloud PT C
Sulfur wt% / Pour PT C
Sulfur wt%
Viscosity cSt / @ °C
RON Clear / Cetane Index / Number
MON Clear /
RON loss in posttreater /
MON loss in posttreater /
Olefins content, % /

HCO Slurry
SG or °API SG or °API
Distillation Type TBP / ASTM Distillation Type TBP / ASTM
IBP °C IBP °C
5% °C 5% °C
10% °C 10% °C
30% °C 30% °C
50% °C 50% °C
70% °C 70% °C
90% °C 90% °C
95% °C 95% °C
FBP °C FBP °C
Sulfur wt% Sulfur wt%
Viscosity cSt / @ °C / Viscosity cST / @ °C /
Operating Problems General Expectations
Unit Limitations: Sales / Technical Service Visits:
Catalyst Circulation: Equilibrium Samples / Month:
Product Quality: Unit Monitoring Reports / Year:
Stack Emission: Quality & Logistics:
Other Problems: Other wishes:

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